Conversion of solid fuels and products derived therefrom or other materials into valuable liquids



' 1,890,434 CTS DERIVED THEREFROM,

IDS

1932. c. KRAUCH ET AL CONVERSION OF SOLID FUELS AND PRODU QR OTHER MATERIALS INTO 'VALUABLE LIQU Filed Feb. e, 1926 2 Sheets- Sheet 1 kmaswqxk tmwkk A in wutkekh my km w an W S 5 M 1 n R P N o a T T S R I m 0 W2 n m m A Dec. 6, 1932. c. KRAUCH ET AL 1,390,434

CONVERSION OF SOLID FUELS AND PRODUCTS DERIVED THEREFROM OR OTHER MATERIALS INTO VALUABLE LIQUIDS I 'Filed Feb. 6, 192 6 2 Sheets-Sheet 2 2 (4 %l N 5 N E Pl/NP lmcno/v wanes/z PUMP msn an! mVENToR's Caz-1 Krauck BY malhias Pie?"- ATTORNEYS Patented Dec. 6, 1932 UNITED STATES PATENT "eoFF-Ica CARL KBAUGH. OF LUDWIGSHAFEN-ON-TEE-RHINE, ND HATEIAS PIER, OF HEIDEL- BERG, GERMANY, ABSIGNORS, BY MESNE ASBIGNIENTS, 'IO STANDARD-I. (3-. COM- rm, 0] LINDEN, NEW JERSEY, A. CORPORATION OF DELAWARE I oomn'sron or semi) roars am) raonucrs nnarvnn rnmraou on ornna 1 MATERIALS rn'ro VALUAIBLE mourns Application filed February 6, 1926, Serial No. 86,846, and in Germany February 14 1925.

for a ong-time been how to produce 'ood gasoline or other valuable liquidfuels rom solid fuel including coal-in all its varieties and wood, and products of distillation, or mineral oils, especially heavy oils.

One attempt at the solution of this problem has been by liquefaction of coals by means of hydrogen or by destructive hydrogenation of tars or oils under high pressure at high temrature, but this has not reached application 1nd'ustrially because of an unsatisfactory speed and rate of the conversion.

By the process herein described we claim to have successfully solved this problem for the first time and to be able to produce good pure liquid fuels, including also benzines from solid fuels and to convert also tars obtained from solid fuels and also heavy mineral oils or residues into more valuable liquid products, including benzines, by \a process economical immaterial, time, labor and wear of apparatus. v

In arrivin at the herein described process we have ma e several discoveries or inventions.-

We will now set forth a general ex lanation'of our process followed by speci c examples thereof with .the understanding that the appended claims are intended to cover the features of the invention expressed therein severally and collectively.

We conceived the idea of applying a catalyst to said solid fuel or other materials, in connection with said hydrogenizing high ressure and high temperature process, but ound that an improvement of the process could not be obtained at all or at least not in a continued operation. J.

Thereafter we discovered that the cause of this drawback was the sulfur present in the treated material, and by experimenting discovered certain catalysts which would work satisfactorily under the existing conditions notwithstanding the resence of the sulfur. or

sulfur compounds. uph catalysts prove valuable not only under high ressure but even under ordinary pressure, t ough high pressure is more suitable, and most advantaously the hydrogenizing gas is employed in I ing materials, and that many troubles in the operation and also other drawbacks were hereby caused, and we discovered that under the conditions existing in the process of h drogenizing, whether with an addition of t e aforementioned or, other catalysts or in the absence of catalysts an apparatus composed of or lined with aluminium would behave excellently. Even with materials rich in sulfur, for example Mexican Panuco oil, aluminmm or its alloys are not attacked by the com tact with hot, gaseous, liquid or solid material, and when using them as a lining they may be used until near their meltin point. Also chromium and alloys therewitii resistant to the attack in the course of the operation in so far as these metals or their alloys are impermeable to as and do not contain free injurious iron. specially chromium itself and alloys containing more than 10 per cent of chromium and not more than 0.2 per cent, preferably less than 0.1 er cent of carbon, are verysuitable. At t e same time a content of nickel amounting to 40 per cent or more makes a very useful material which is not attacked even if in use for a very lon time. I

e further discovered that the process according to the present invention 18 in many cases, and in particular when convertin solid fuels or heavy oils or residues, great y improved by carrying out the process in two parts or stages. In thefirst stage the'coal, tars or heavy petroleum products are converted into liquids poor in fractions of low boiling point by liquefaction or destructive hydrogenation with or without catalysts, while in the second stage the products of sta e one are transfirmed into hydrocarbons of ow boilin point, by destructive hydrogenation, but pre erably with the aid of catalysts. Increased pressure, is preferably employed in one or oth stages. Insofaras catalytic masses are added in both stages, they may be of the same prove kind. or different in quantity, concentration, or kind. The two sta es can be efiected in two se arate or adjoining reaction vessels or r in di erent parts of a single vessel constructed in a suitable manner. Even more than two stages may be employed successively in certain cases.

The catalysts most suitable to be added for effecting the said conversion must be of a nature substantially immune to sulfur poisoning in this process and can be of varied character. As examples we quote compounds of nitrogen, or combined sulfur, partlcularly sulfids of heavy metals, also molybdenum, tungsten, chromium and uranium which are here referred to as metals of the sixth group .of the periodic system or compounds 0 sue metals. Other catal sts immune from sulfur poisoning may also e used or more than one such catalyst at the same time or successively, or mixtures of such catalysts with other bodies. Other com ounds acting in a different way, for examp e, as splittin agents, and inert solid bodies may also be ad ed.

As examples of compounds of nitrogen to be added to the materials which are to be brought into reaction, we mention ammonia, or ammonium sulfid, or nitrides, for example silicon or titanium nitrides which are comparativel stable to water. Several compounds 0 nitrogen of different character, for exam le solid and gaseous compounds as nitri es and ammonia may be used at the same time. Instead of nitrogen compounds,

free nitrogen may be added to the hydrogen gas in the presence or with an addition of catalysts capable of synthesizing ammonia, but ammonia or other compounds of nitrogen may also be added simultaneously.

When employing combined sulfur, it may be added in different forms, for example of sulfides, single or mixed, also in mixture with metals, such as silver, molybdenum, tungsten or cobalt or oxids, such' as those of magnesium, calcium, zinc, aluminium titanium, zirconium, cerium, thorium, vanadium, chromium, molybdenum, tungsten, uranium,

manganese or cobalt or hydroxids such as those of calcium, aluminium, thorium, chromium, manganese or cobalt or carbonates such as those of lithium, beryllium, magnesium, calcium, zinc, manganese or cobalt and the like, especially in mixture with catalysts promoting hydrogenation. Sulfids of heavy metals, particularly those of the iron group, whether alone or in mixtures, are of special efliciencya Sulfur may also be introduced in other forms, for example by adding sulfites or sulfates, or adding free sulfur to metal oxids such as those of zinc, vanadium, molybdenum, tungsten, uranium, manganese or cobalt and the like and thereby generating a catalyst containing combined sulfur. Also by treating iron with sulfuretted hydrogen at an elevated temperature, a catalyst of last in efliciency can be produced.

hen using metals of the sixth group of. the eriodic system or compounds thereof as cata ysts, the latter may comprise, for exam le, molybdenum or other related metal as ree metals or compounds, such as Sulfids, "or molybdic acid, or ammonium inolgbdate, and these substances ma be emplo e either alone or in mixture wit other bo ies which may possess hydrogenating properties, or not. For example, cobalt or iron, or compounds thereof, or alumina, zinc oxid, magnesia, or calcium carbonate may be cited as additions to the said catalyst immune to sulfur poisoning. The said catalysts may be employed on --pe'r, cadmium, lead, bismuth and tin, lithium oxid or carbonate, magnesite, boric acid. alumina, rare earths, ditficultly reducible oxids of the metals of the fourth group, oxids or carbonates of zinzc, manganese and vanadium, diflicultly reducible oxids of other metals, and combinations of two or more ofthe above mentioned metals, as such, or in the form of their, compounds, for example, a mixture of copper and zinc or a mixture of silver and chromium or a mixture of compounds of said metals with or without additional catalytic elements, especiall iron or other metals of the iron group. (i catalysts suitable to give rise to methanol from hydro en and an oxid of carbon can be employed, and is is preferable in such cases to employ mixtures of hydrogen and an oxid of carbon or to use steam.

The said catalysts may-be added in any suitable manner. They may be added to the solid or liquid material, or in the case of liquids they ma be placed into the reaction vessel and the liquids brought into contact with them in a vaporized or otherwise finely enerall 1 invention can be applied to any sort of solid fuels, for example, hard or soft coal, brown coal, lignite, peat, wood, or similar materials, mineral oils, shale oils, or other solid or liquidbitumina, also distillation or extraction products of all of them, such as tars obtained from them, whether by ordinary destructive distillation or by low temperature carbonization, or brown coal bitumen, or tars -or oils obtained by pressure hydrogenation conversion products of all above mentioned.

materials, such as cracked products, coumarone or any other resins or residues of their distillation pitch, asphaltum and so on, or mixtures of several such products with each other, also of solids with the above named liquids or of one or more of such products with other suitable organic liquids.

Especiall when employing coal. or li uid fuels, an a dition of ligmte or peat is o ten of advantage, often increasing the hydrogenizing action, avoiding several drawbacks and in the case of solid substances rendering their introduction easier. All the said materials may housed in the presence of substantial amounts of water and, if desired, water ma be added as such. .Sometimes the process 0 h drogenation is hereby furthered. For examp e lignite producer tar containing from 40 to 50 per cent of water may be used to advantage directlfy.

The preferred form 0 carrying out the process is generally a continuous operation with a stream'of the gases and with an excess thereof over the required quantity and preferably while maintaining the desired pressure by adding fresh gas and passing the gas either by circulation through one or more reaction vessels or through a succession of several reaction vessels. The material to be converted is supplied at the proper place and the products are separated from the reaction gases by cooling.

The gases serving for the reaction may consist of hydrogen alone or of mixtures containing hydrogen, for example a mixture of hydrogen with nitrogen, or water gas, or hydrogen mixed with carbon dioxid hydrogen sulphide, water vapor or met ane or other hydrocarbons. Or the hydrogen may be generated in the reaction chamber by the interaction of water and carbon monoxid, and the like. When employing nitrogen, compounds as catalysts, and carbon monoxid and water, the gas must be employed in a stream.

The hydrogen, gases required for the destructive hydrogenation can be obtained in anysuitable manner; among other methods the following may be mentioned.

Gaseous or vaporized hydrocarbons, whether alone or mixed with each other or other gases are decom osed at a high temperature with a suitab y restricted quantity of oxygen or a gas rich in oxygen so as to combine substantially only the carbon contents with oxygen producing carbon monoxid and setting free the hydrogen. Water vapor orcarbon dioxid or both may be added to the oxygen and catalysts may be employed in order to facilitate the partial combustion, for example nickel coated magnesia or other solid bodies, or fused iron or iron alloys. The

carbon monoxid may thereupon, when found desirable, be catalytically brought into reaction with steam 1n order to produce more hydrogen. As in the process of liquefaction I or destructive hydrogenation of coal and other materials, methane and other simple hydrocarbons are produced, the gases obtained in the reaction or the hydrocarbons isolated therefrom may serve for the said decompositon, preferabl after the more valuable higher gaseous ydrocarbons, for example ethane or propane, have been removed by means of cooling or suitable absorbents and recovered for other uses. The decomposition with oxygen may also be effected at an elevated pressure with special advantage when making use of the gases resultin from the hydrogenation process, in whic case the decomposition may be effected at a pressure identical with or lower than that prevailing in the hydrogenation in order to save compression energy.

The process is best carried out under elevated or even strongly elevated pressure and most suitably with a stream of the gas passed through or over the material to be treated or carrying it along through the reaction vessel by which method the production ob tained by the process is very large.

Depending on the condition of working, for example temperature and pressure employed or duration of the treatment, the products are poor or rich in products of low boiling point. Generally the temperature ranges between 300 and 700 degrees centigrade, and when working under pressure, it should amount to 20, 50 or more atmospheres.

Compounds obtained by the aforedescribed hydrogenation treatment of solid fuels, tars, mineral oils and other materials referred to, which compounds may be comprised by the term destructively hydrogenized fuels are generally very low in sulfur or even completely free therefrom and are excellently suitable for use as fuel for internalcombustion engines. These destructively hydrogenized fuels, whether obtained as aforedescribed or otherwise, may be mixed with one or more other liquid fuels, for example, benzi-nes or gasoline obtained by the cracking process, benzol or low alcohols of the aliphatic series and possess the remarkable property of being miscible with the latter, particularly with methanol, to a large degree. Such mixtures are also useful as fuels for internal combustion engines. A mixture composed of 60 per cent, by weight, of a hydrocarbon obtained from lignite, 30 per cent of gasoline and 10 per cent of methanol maybe cited as an exam le. The destructively hydrogenized fuels, however produced, are also valuable as solvents for various purposes for which they may be used either alone or in conjunction, with other bodies. Theyexcel by being miscible with .portion with t e synthetic benzines. They are also excellent solvents for many purposes.

In the accompanying drawings, an apparatus for carrying out the one stage process and an apparatus for carrying out the two stage process, both being continuous, are 11- lustrated diagrammatically, partly in vertical section. Our infizntion is not limited to the apparatus illustrated therein, however, but may e varied at will in accordance with the conditions of working.

Referring to the drawin s in Fig. 1 in detail, reference numeral 1 indicates a feed line from any convenient source of liquid raw material. The line. 1 discharges to a grinding mechanism 2 fitted with a hopper 3 through which solid materials may be admitted. If desired, the grinding mechanism can be by-passed by line 1a when no solid materials are used. The suspension of solid material in liquid or the liquid alone may be then forced by pump 5 througha line 4: to a heat exchanger 6 and thence by line 7 into a reaction chamber 8. The reaction chamber is constructed in any preferred manner and should be adapted to withstand high pressures, for example; above 20-100 or even as high as 800 atmospheres, as well as the corrosive effects of the reactants. The vessel is preferably protected from loss of heat by a suitable insulating cover 9 and-may be heated by electric coils 10 which are arranged within the drum. The contents of the drum are preferably kept in a state of agitation by means of a stirring mechanism 11 and, if desired, suitable catalytic materials 11 as indicated above may be attached to the stirring mechanism so that the catalyst is brought into intimate contact with the contents of the vessel.

Hydrogen under high pressure is forced through a line 12, heat exchanger 13 and then by line 14 into the base of the reactor 8 into which it is preferably discharged through a spray pipe 15. A liquid level may be maintained in the drum, for example at the point 16a and gas and vaporous products may be continuously withdrawn by vapor line 16 which is in communication with exchanger 13 and a cooling coil or condenser 17 The condensate and'gasis discharged into'a sepa ration drum 18 from which the distillate is removed byline 19 to storage, not shown. The gas may be taken off by a pipe 20 to a purifying system indicated at 21, and which maycomprise a scrubbing system preferably carried out at high pressure using, for example, soda to remove hydrogen sulfide and oil to remove hydrocarbon constituents from the gas. Purified gas is then recompressed 4 steps. Where possible, the same numeral has been used in Fig. 2 as has already been indicated in Fig. 1. Hydrocarbon oil is withdrawn from any suitable storage, not shown, by a line 1 and may be forced through a rinding mechanism 2 which is fitted with t e hopper 3 for the introduction of solid material, such as coal, lignite or the like. The pump 5 forces this mixture through line 4 into the first oven indicated by the numeral 8a. This oven may be constructed in the same manner as the oven 8 shown in Fig. 1 and similar parts are designated by the same numerals. A heavy liquefied material is withdrawn from the base of the oven 8a and may be continuously discharged into the second oven indicated by 8b. This oven may be packed with a suitable solid catalytic material indicated at 11' and with the exception that no stirring mechanism is used it may be constructed similarly to oven 8a.

Hydrogen is forced under high pressure from the line 12, as before, through a heat exchanger 13 and by line 14 and branches 14a and 14b into oven 8a and 8?) respectively. Vaporous products and gas are removed from both ovens by vapor line 16a and 16?; respectively which may discharge through a single exchanger 13 to condenser 17. The light oils are separated from the gases in the separator 18 from which the oil is removed by 19 and the gases may 'be'removed, purified and recompressed as indicated in Fig. 1. Heavy oil may be continuously withdrawn from the oven 8?) and a part or the whole thereof may be continuously discharged through a line 24a, cooler 26 and conducted by line 25 to any suitable storage. If desired, a part of this oil may be re-circulated to line 1 or to line 4 by means of recirculation line 24b, pump 27 and either of the two lines 28 or 29, as is desired.

In the operation of this system solid carbonaceous material containing ash may be continuously fed to the first oven and asufiicient quantity of the oil containing inorganic material may be led from the system by the lines 24a and 25 so as to prevent accumulation within the system. Fresh hydrocarbon oil may be continuously fed in sufficient quantity to carry in the solid material or if desired,'a part of the oil withdrawn from the second oven, either containing ash or from which the ash has been removed by 4 ditions.

filtration, settling centrifugal means or the In the following examples the time of reaction varies considerably, as might be supposed, depending on the nature of the raw.

material, the activity of the catalyst, temrature, pressure and the like. In practice it is desirable to make a few preliminary runs in order to determine the time required for the best yields under a given set of con- 4 Generally speaking, with batch operations the total time may be from two to ten hours or more, depending on the yield desired, while with continuous operations the time is usually shorter. When continually feeding liquid or difiicultly vaporizable oils, the rate of flow may be in the neighborhood of .3 to .8 volumes of oil per hour per volume of reaction space. Vaporous materials may be treated at higher temperatures and the feed rate may consequently be one or even one and one-half volumes per hour per volume of reaction space. The volume of hydrogen may likewise vary considerably and should always, of course, be in excess of that actually required for the conversion; for ex ample, the rate of flow of hydrogen may be in excess of about 600 litres per kilogram of carbonaceous material.

The following examples will serve to further explain how our invention is carried out in practice, but we do not restrict our invention to these examples.

Example 1 .Brown coal dried in the air is introduced in a continuous manner into a vessel capable of withstanding high pressure and heated to about 500 degrees centi grade and exposed therein to the action of a stream of hydrogen in excess of the required amount and brought under a pressure of 100 atmospheres, after van addition has been made to thegas oil per cent by volume, of ammonia. The products of the reaction are carried away with the gas current and condense by. cooling after leaving the furnace, whereby a thin oil with but little phenolic bodies is obtained. In the end 80 per cent or more of the carbonaceous matter contained in the brown coal is liquefied and at the same time 10 per cent of gaseous hydrocarbons are formed.

The conditions of working may be varied to a large extent; the pressure may be lower or higher. In addition to ammonia other catalysts, or solid bodies may be employed,

for example, iron, cobalt, or the like, or por-.

ous lumps of clay, adding them to the coal or arranging them separately. The brown scribe coal may be mixed with a liquid, for example, with part of the product obtained as de- E'mantple 2 A vessel suitable to withstand high pres sure is supplied withpieces of pressed aluminium hy roxid and heated to a out 500 degrees centigrade and a gas mixture composed of. 79 per cent, by volume, of hydrogen, 20 per cent of nitrogen and 1 per cent of ammonia, charged with the vapors of dehydrated brown coal producer tar at a low partial pressure is led through under a pressure of- 200 atmospheres. On cooling the gases leav ing the vessel, a product containing thin' liquid hydrocarbons is obtained, which is practically free from oxygenated and unsaturated compounds. The residual gas mixture may be returned to the reaction vessel after replacing the consumed hydrogen and removing gaseous hydrocarbons which are formed to a small extent. 1

When employing titanium nitrid instead of ammonia and aluminium hydroxid, and

the above gas mixture or hydrogen alone, under similar condltlons, a. product containing about 70 per cent its weight of gasoline boiling up to 200 degrees centigrade is obtained.

Mixtures of coals and tars or of coal or tar with products of the hydro enation of such materials or with other suitable liquid diluents may also be employed.

Ewample 8 and proceeds at a constant velocitg. In the product obtained by cooling, the p ols'are largely reduced to hydrocarbons.

Similarly, when treating coal tar or brown coal tar or raw distillates thereof, phenolic bodies contained therein are reduced to h drocarbons to a satisfactory degree notwitli standing the presence of hydrocarbons and impurites such as sulfur compounds,pyridine and the like; unsaturated compounds are converted into saturated ones, mobile valuable oils being thus formed in a continuous operation without formation of asphaltum or coke.

- In the above example, cobalt sulfid ma be replaced by a mixture of thesulfids of co alt and nickel, or of cobalt and man anese, or of cobalt and iron, or by zinc sulfi or aluminium sulfid, or other catalysts containing combined sulfur. i

Example 4 Brown coal is intimately mixed with -1 per cent its weight of m'olybdic acid and introduced into a vessel capable of withstanding high pressure, in which it is treated at about 500 degrees centigrade and under a ressure of 150 atmospheres with a steam 0 hydro- Example Brown coal tar obtained in a gas producer fed with brown coal, is vaporized at a temperature of 500 degrees centigrade and under a pressure of about 150 atmospheres, in a current of hydrogem and the mixture is continuously passed over a contact mass consisting of a mixture of molybdic acid with an addition of per cent its weight of aluminium hydroxide. .The gas is pumped round in a circular way while maintaining the pressure by an addition of fresh hydrogen, and separating, the material by cooling. There is formed a mobile and nearly colorless product free from phenols, without any'formation of coke, asphalt or other residue. From thirty to fifty per cent of the product distil up to 150 degrees centigrade, and the fractions up to- 300 degrees centigrade are colorless and fully saturated. At 350 degrees centigrade only a small residue is left having a Vaselinelike nature. The raw product can be used as a motor fuel or for manufacturing lubrieating. oils. An addition of say 1 per cent of ammonia to the hydrogen is also useful.

A mixture consisting of 75 per cent, by volume, of hydrogen and per cent of nitrogen may also be used, preferably at a pressure of '200 atmospheres.

Molybdic acid alone or molybdenum sulfid or other masses containing molybdenum may also be employed. also coal tar, and components such as raw cresylic acid.

Eieample 6 degrees to 550 degrees centigrade whereby it is rapidly and completely converted into hydrocarbons.

Example 7 Petroleum residues when treated as described in the foregoing example yield in a continuous manner and without any formation of coke or asphaltum, at between 450 degrees and 500 degrees centigrade, a product containing from to 80 per cent of benzene boiling up to 150 degrees.

Example 8 Brown coal tar obtained in a gas producer is continually passed, along with a mixture of 3 parts of hydrogen with 1 part (by volume) of nitrogen at about 500 degrees centigrade and under 200 atmospheres over a catalyst consisting of chromium hydroxid. The tar is hereby converted into a mobile oil, practically free from phenol and of a saturated nature and containing about 50 per cent of benzine (boiling up to 150 degrees centi grade) The fractions of higher boiling point are free from asphaltum and can be converted into benzine by a repeated treatment.

Ewample .9

Lignite, whether alone or mixedwith mineral or tar oil, is continuousl fed into a high pressure reaction vessel in w ich it is exposed to the action of a current of hydrogen in excess of the consumed quantity under a pressure of 200 atmospheres and at a temperature of about 480 degrees, while the solid or pasted material is slowly moved forward through the reaction vessel. The hot gas current containing the products formed by the interaction with hydrogen is assed into a second reaction vessel also capa le of withstanding the pressure, which latter is maintained and which vessel is supplied with precipitated calcium carbonate in lumps and heated to from 500 degrees to 550 de rees centigrade whereupon the gases are coo ed after having transferred heat to the gas entering the first vessel; a mobile oil collects in the cool receiver containing about 50 per cent, of benzine of low boiling point. The gas is freed from gaseous hydrocarbons which are present in a small amount and is then passed with an addition of fresh hydrogen to make up for the consumed amount thereof, by means of a circulating pump, successively through the first and second vessel and the cooler. and so forth.

'The solid residue, chiefly ashes, left by the treatment of the brown'coal is suitably withdrawn between the first and second vessel. By this treatment or more per cent of the carbon contents of the lignite is easily and quickly converted in a continuous manner into valuable hydrocarbons.

A catalyst of the character described above may also be employed in the first stage, and in the second stage the calcium carbonate may be replaced by other such catalysts and those of a more precious character are preferably employed in the second stage where there are no ashes or other solid residues.

Example 10 Dark colored residues of an American rock oil which at ordinary temperature are nearly solid and have a strongly unsaturated character are incorporated with an excess of a gas mixture composed of three parts, by volume, of hydrogen and 1 part of nitrogen and continuously passed under a pressure of 200 atmospheres and a temperature of from 450 degrees to 500 degrees Centigrade over a catalyst prepared from an intimate mixture of 70 parts, by weight. of ammonium molybdate and 30 parts of aluminium hydroxid. A nearly colorless, mobile and saturated product is obtained besides a little methane,

consisting of 90 per centiof colorless petrol boiling u to 150 degrees and 10 er cent of a thin, ye owish product of a hig er boiling point.

E'wample 11 Jura shale oil of 0.950 sp. containing 4 per cent of sulfur which on dlstilllng yields per cent of a pitch-like residue over 350 degrees centigrade is treated as described in the foregoing example. The product. is a mobile yellowish oil of 0.810 sp. gr. containing per cent of saturated petrol boiling up to 150 degrees and leavin at 200 degrees centigrade a liquid only s "ghtly colored Example 12 Mexican asphaltum is dissolved in its own weight of cyclohexa'ne and treated in the aforedescribed manner. The cyclohexane is recovered unaltered, while the asphaltum which before the treatment contained 4 per cent compounds boiling up to '250 degrees centi rade,25 per cent more boiling up to 350 egrees centigrade and 70 per cent of a hard pitch residue is converted into a mobile oil, free from oxygen compounds and chiefly consistin of petrol hydrocarbons besides a very sma lvaseline-like residue.

'Rock oils of any origin may be treated as residue.

described in the above examples and thereby converted into refined products of much more valuable properties.

Ea'ample 13 Dark-colored residues of an American rock oil which at ordinary temperature are nearly pheres and a temperature of from 450 degreesto 500 degrees centigrade.

The product which is formed besides a little methane is a slightly yellowish liquid of 0.800 or less sp. gr. which on distillation yields about 50 per cent of gasoline boiling up to 150 degrees centigrade of saturated character, up to 250 degrees centigi'ade additional 28 per cent dis tillage and leaves at 325 degrees centigrade 'about- 5 per cent of a thick or Vaseline like only slightly colored residue.

With's ilicon or titanium nitrid instead of activated iron and the above gas mixture or pure hydrogen a similar result is obtained.

' Example 14 Dark-colored residues of an American rock acter,-are incorporated with hydrogen and additional 35 per cent up to 350 degrees centigrade all of a saturated character. The small residues are thick or Vaseline-like and free of pitch, Y

7 Example 15 Steamer fuel oil, produced from American oil, is passed in a continuous manner, together with a'mixture of hydrogen and nitrogen, at about 500 degrees centigrade and under a pressure of 200 atmospheres over a catalyst prepared by impregnating porous material'with lead nitrate. The gas is circulated while .maintaining the pressure and making up for the consumed hydrogen by fresh'gas. A light-colored product of 0.85 sp. gr. is produced, the lower fractions of which 'may directly'serve as a fuel for internal combust'on engines, while the higher fractions are a high-grade starting m'a'erial for preparing lubricating oil.-

Instead of lead nitrate, stannous chlorid,

whether single or mixed with each other or with compounds oi iron, cobalt and others,

may also be used, and other materials such as tars, coal, etc. may be treated in a similar way. r

Example 16 Cresylic acid obtained from coal tar is continuously passed along with a mixture of hydrogen and nitrogen at about 450 degrees centi grade and under a pressure of about 150 .atmospheres over a catalyst containing the oxids of silver and titanium. The phenolic bodies are hereby completely reduced to hydrocarbons. Catalysts comprising lithium carbonate, magnesite, manganese oxid, silver borate, or copper and cerium oxid, or silver and cobalt oxid can be used similarly.

Example 1? Brown coal producer tar is cont'nuously passed together with a current of hydrogen,

under a pressure of 800 atmospheres and at a temperature of about 500 degrees centigrade over a catalyst consisting of porous material coated with vanadic acid. The product obtained consists of up to 50 per cent of gasoline.

A catalyst containing thoria or a mixture 6 p cent pe p to 150 degrees and 21 dper cent, of a fractlon up to 150 degrees of compounds of uranium and z'nc or of copper and zinc or of silver and tungsten or of silver and silicon 'or others with or with-v out a carrier may also be used.

Example 18 Two parts of liguite producer tar a re mixed with 1 part (by weight) of raw hgnite or peat and continuously forced 111120 a high pressure vessel and treated therein with hyabout 25 per cent of a gasoline fraction is obtained, the high boiling fractions of which may be subjected to a repeated treatment or utilized in any other manner, for example for the production of lubricating oils or solvents or washing means or impregnating oils or insulating oils. The hydrogen is pumped around while the residue containing ashesand mostly a little carbon is slowly discharged as a paste. The gas current may be so rapid that the gases of the reaction carry enough of the products to be subjected to a second or even third or more treatments in subsequent vessels. If in the second vessel a catalyst containing molybdenum is employed, over which the reaction gases pass at about 500 degrees centigrade, a product with 50 per cent of a petrol fraction is readily obtained with a complete reduction of phenolic bodies and an extensive removal of sulfur.

An addition may be made to the starting material of roasted pyrites orother contact bodies.

Example 19 Vaporized brown coal tar is incorporated with a gas mixture composed of 10 per cent, by volume, of carbon monoxid and'90 per cent of hydrogen and brought under a pressure of 200..atmospheres, and the mixture is passed at about 450 degrees centigrade over a catalyst suitable for the synthesis of methanol prepared from 9 parts of zinc oxid and 1 part of chromic acid. On cooling, 2. product is condensed which contains some methanol and oxygen compounds of a higher order, about 30 per cent of benzine and products of a higher boiling point which may serve for a conversion into lubricating oils or for a repeated treatment as aforementioned. The mixture of hydrogen and carbon monoxid is circulated while replacing the consumed gases. I

In all of the above examples the hot parts of the apparatus may be lined or coated with aluminium or aluminium alloys or chromium or made or coated with an alloy of 60 per cent of nickel, 27.7 percent of iron, 12 per cent of chromium and 0.3 per cent of carbon; or an alloy composed of 58 per cent of nickel, 25

percent of iron, 17 per cent of chromium and 0.03 per cent of carbon; or an alloy composed of 96 per cent of iron, 1.75 per cent of nickel, 1.5 per cent of chrominum, 0.1 per cent of carbon and'also of 0.25 per cent'of silicon,

,027 per cent of manganese, besides small distillation and extraction products therei of is intended to relate only to normally solid and liquid. distillation and extraction products and is not to be construed to include normally gaseous products of the distillation of solid and liquid fuels.

Likewise when the expression containing a metal of the sixth group is used it is intended to mean such metals in the free and in the combined state.

Also when the expression added catalyst is used in said claims it is not necessarily intended to mean that a catalyst is introduced into the reaction chamber with each charge of carbonaceous material but is merely intended to indicate that the reaction is carried out in the presence of an effective quantity of a catalytic, material which is not naturally contained in the carbonaceous material'under,

going treatment or is contained in said car-" and liquid fuels. distillation and extraction products thereof, into valuable liquids which comprises treating them with added hydrogen in the presence of an added catalyst immune to sulfur poisoning, and heat at a temperature suflicient to promote the conversion and at a pressure of at least 20 atmospheres.

2. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels. distillation and extraction products thereof. into valuable liquids which comprises treating them with added hydrogen in the presence of an added solid catalyst immune to sulfur poisoning, andheat at a temperature sufiicient to promote the conversion, and at a pressure of at least 20 atmospheres, the conditions of working, such as temperature. pressure, and the efliciency of the catalyst being so adapted to each other,

. as to give rise to the formation of substantial amounts of low boiling hydrocarbons of a benzine character.

7 distillation and extraction products thereof,

into valuable liquids by destructive hydrogenation which comprises treating them with hydrogen and a catalyst containin molybdenum at a temperature upwards of 350 C.

5. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction productsthereof, into valuable liquids which comprises treating them with added hydrogen, and a catalyst containing a metal of the sixth group of the periodic system, and heat at a temperature sufficient to promote the conversion and elevated pressure of at least 20 atmospheres.

6. The process of destructively hydrogenizing carbonaceous substances, such as solid' and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with hydrogen and a catalyst containin a temperature 'su cient to promote the conversion at a pressure of at least 20 atmospheres.

7 The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable li uids which com rises treating them with ydrogen under increased pressure of the order of 200 to 800 atmospheres at temperatures of the order of 400 to 550 C. while confined in a vessel of adequate strength the surfaces of which exposed to the reacting materials have a degree of resistance to attack by hydrogen and sulphur, under the conditions of temperature and pressure given and in the presence of the reaction products, not substantially less than that of an alloy of iron containing 10 percent of chromium and .2 percent of carbon.

8. A process for converting carbonaceous substances such as solid and liquid fuels, distillation and extraction products thereof, into 7 valuable liquids by destructive hydrogenation in a reaction vessel the inner surface of which comprises chromium at a pressure of at least 20 atmospheres.

9. A process for converting carbonaceous substances such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids by destructive hydrogenation in a reaction vessel the inner surface of .which is made of an alloy of chromium at a v molybdenum and heat at.

tion in a reaction vessel the inner surface of. a

which is made of an alloy containing at least 10 per cent of chromium at a pressure of at least 20 atmospheres.

prises employing hydrogen and an oxid of,

carbon and an added catalyst capable of combining hydrogen and the oxid of carbon to methanol and heat at a temperature sufiiclent to promote the conversion and at an elevated pressure of at least twenty atmos 'pheres.

13. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with hydrogen and a catalyst immume to sulfur poisoning, in the presence of a substantial amount of water, and heat at a temperature sufficiently high for the conversion and at a pressure of at least 20 atmospheres.

14. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids, which comprises treating them with added hydrogen in the presence of an added solid catalyst immune to sulphur poisoning, and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 20 atmospheres.

15. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids, which comprises treating them with added hydrogen in the presence of an added catalyst immune to sulphur poisoning, and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 20 atmospheres, the conditions of working, such as temperature, pressure and etficiency of the catalyst, being so adapted to each other as to give rise to the formation of substantial amounts of low boiling hydrocarbone of a gasoline character.

16. The process of converting carbonaceous substances, such as solid andliquid fuels, distillation and extraction products thereof into valuable liquids, which comprises treating them with added hydrogen and an added catalyst immune to sulphur poisoning, and heat at a temperature of between about 300 and 7 00 C. and at an elevated pressure of at least 100 atmospheres.

17. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof into valuable liquids, which comprises treating them with a stream of hydrogen and an added catalyst immune to sul hur poisoning, and

.heat at a temperature between about 300 and 700 C. and at an elevated pressure of at least atmospheres.

18. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids, which comprises treating them with added hydrogen and a catalyst comprising a metal of the sixth group of the periodic s stem and heat at a temperature of I between a out 300 and 7 00 C. and at a pres- 20. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids, which comprises treating them with hydrogen and a catalyst containing molybdenum, and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 20 atmospheres.

21. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation andextraction products thereof, into valuable liquids, which comprises treating them with hydrogen and a catalyst containing molybdenum, and heat at a temperature of between about 300 and 700 C. and at a pressure of more than 50 atmospheres.

22. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into them with hydrogen in a stream, and a catalyst containing molybdenum, and heat at a temperature of between about 300 and 700 C. and at an elevated pressure upwards of 100 atmospheres.

7 00 C. and at a pressure of at least 20 atmospheres. v

24. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products between about 300 and thereof, into valuable liquids, which coniprises treating them with hydrogen and a catalyst immune to sulphur poisoning, in the presence of a substantial amount of water, and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 50 atmospheres. I

25. The process of roducing liquids from solid fuel materials w ich comprises destructively hydrogenating the initial material in the presence of an added catalyst immune to sulphur poisoning at a pressure of at least 20 atmospheres and at a temperature of between about 300 and 700 C.

26. The process of producing liquid hydrocarbons from coaly material which comprises destructively hydrogenating the initial material in the presence of an added catalyst immune to sulphur poisoning at a pressure of at least 20 atmospheres and at a temperature of between about 300 and 7 00 C.

27. The process of producing liquid hydrocarbons from lignite which comprises destructively hydrogenating the initial material in the presence of an added catalyst immune to sulphur poisoning at a pressure of at least 20 atmospheres and at a temperature of between about 300 and 700C.

28. The process of converting. carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids, which comprises treating them with hydrogen and a catalyst containing a metal of the sixth group of the periodic system, and heat at a tcmper-- ature of between about 300 and 700 C. and at an elevated pressure of at least 50 atmosceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids, which comprises treating them with a continuous stream of hydrogen and a substantial amount of water and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 50 atmospheres in the presence of a valuable liquids, which comprises treating icatalyst immune to Poisoningby Sulphur- 30. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof into valuable liquid products, which comprises treating a mixture of a solid fuel of a more recent geological age than coal with another carbonaceous material by destructive hydrogenation in the presence of a catalyst immune to sulphur poisoning under a pressure of at least 20 atmospheres and at a temperature between about 300 and 7 00 C.

31. The process of destructively hydrogenizing carbonaceous substances, such as'solid and liquid fuels, distillation and extraction products thereof into valuable liquids, which comprises first treating them with hydrogen at a pressure of at least 20 atmospheres and with heat at a temperature sufiicient to 'promote the conversion until roducts poor in fractions of low boiling point are obtained, and then in a further stage converting the heavier fractions of such products alone into products rich in fractions of low boiling point by a further treatment with hydrogen at a pressure of at least 20 atmospheres and heat at a temperature sufiicient to promote the conversion, in the presence of an added catalyst immuneto sulphur poisoning. v

32. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extract on products thereof into valuable liquids, WhlCh comprises first treating them with a current of hydrogen at a pressure of at least atmospheresand with heat at a temperature suflicient to promote the conversion until products poor in fractions of low boilmg point are obtained, and then in a further stage converting the heavier fractions of such products alone into products rich in frac tions of low boiling point by a further treatment with hydrogen at a pressure of at'least 50 atmospheres and heat at a temperature sufiicient to promote the conversion in the presence of an added catalyst immune to sulphur poisoning.

33. The process of converting carbonaceous substances, such. as solid and liquid fuels, distillation and extraction products thereof into valuable liquids, which comrises first treating them with a current of liydrogen at a pressure of at least 50 atmospheres and with heat at a temperature of between about 300 and 700 C. until tarlike products poor in fractions of low boiling point are obtained, and then in a further stage converting the tar-like products alone into products rich in fractions of low boiling point by a further treatment with hydrogen at a pressure of at least 50 atmospheres and heat at a temperature of between about 300 and 700 C. and in the presence of a catalyst.

34. The process of destructively hydrogenizing carbonaceous substance, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with hydrogen in the presence of an added solid catalyst immune to sulphur poisoning, at a temperature sufiiciently high for the conversion and at a pressure of at least 20 atmospheres for a period such that, under the conditions as above given, the product is substantially free from asphalt. v

35. The process of destructively hydrogenizing. carbonaceous substances such as, solid and liquid fuels, distillation and extraction products thereof, containing asphaltic hydrocarbons, into valuable liquids, which comprises treating them with. hydrogen in the presence of an added solid catalyst immune Q} to sulphur poisoning, at a temperature sufficiently' high for the conversion and at a pressure u wards of I00 atmospheres for a period suc above given, the product is substantially free from asphalt.

36. The process of converting carbonaceous substances such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises continuously feeding said substances with hydrogen into a reaction space containing a solid that, under the conditions as catalyst immune to sulphur poisoning and held at a temperature of between about 300 and 7 00 C. while maintaining a pressure of at least 20 atmospheres in said space and continuously removin resultin products.

37. The process 0 destructively hydrogenizing carbonaceous substances suchas solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with a stream of hydrogen in the presence of an added solid catalyst immune to sulphur poisoning, and heat at a temperature sufliciently high for the conversion and at apressure of at least 20 atmospheres and carrying'off resulting products in the stream of hydrogen.

38. The process of converting carbona- I ceous substances such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with a stream of hydrogen in the presence of an added solid catalyst immune to sulphur poisoning, and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 20 atmo heme and carrying off resulting roducts 1n the vapor state in the stream 0 h drogen.

39. The process of destructively hydrogenizing carbonaceous substances such as solid and liquid fuels, distillation and ex: traction products thereof, into valuable liquids which comprises treating them with a stream of hydrogen in the presence of an added solid catalyst immune to sulphur poisoning, and heat at a temperature sufficiently high for the conversion and at a pressure of at least 20 atmospheres, carrying off resulting products in the vapor state in the stream of hydrogen and cooling the mixed vapors whereby the liquefiable portions of the said products are substantially completely removed from the hydrogen.

40. The process of destructively hydrogenizing carbonaceous substances, such as solid and li uid fuels, distillation and extraction pro ucts thereof, into valuable liquids which comprises treating them with a stream of hydrogen in' the presence of an added -solid catalyst immune to sulphur tploisoning, and heat at a temperature sufciently high for the conversion andat a pressure of at least about 200 atmospheres, carrying off the resulting products in the in the mixed vapors, whereby normally liqui products are separated, removing gaseous hydrocarbons from the stream of hydrogen and returning the hydrogen to the reaction zone.

41. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises continuously feedmg the said substances with hydrogen into areaction space containing a solid catalyst 1mmune to sulphur poisonin and held at a temperature sufiiciently big for the conversion while maintaining a pressure of at least 20 atmospheres in said space, the conditions 'as above given being ad usted to permit of continuously removing resulting products substantially free from asphalt.

42. The process of converting carbonaceous substancessuch as solid and liquid fuels, distillation and extraction products thereof, containing as haltic hydrocarbons, into valuable liqui s which comprises continuously drogen in the presence of an added solid catalyst immune to sulphur poisoning, and heat at a temperature sufliciently high for the conversion and at a pressure of at least 20 atmospheres and carrying off resulting products substantially free from asphalt inthe stream of hydrogen.

44. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises.treat- 111g them with a stream of hydrogen in the presence of an added solid catalyst immune to sulphur poisoning, and heat at a temperature of between about 300 and 700 C. and

at a pressure of at least 20 atmospheres, the condrtions as above given being adjusted to permit of continuous withdrawal of reaction products substantially free from asphalt, withdrawing such products admixed with the hydrogen stream, separating the reaction product from the hydrogen and returning the hydrogen to the reaction zone.

45. The process of converting carbonaceous substances, such as solidand liquid fuels, .distillation and extraction products thereof, into valuable liquids which comprises treating them with added hydrogen and a catalyst comprising a compound of a metal of the sixth group of the periodic system and heat at a temperature between about 300 and 700 C. and at a pressure of at least 20 atmospheres.

46. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises continuously feeding said substances with hydrogen into a reaction space containing a compound of a metal of the sixth group of the periodic system and held at a temperature between about 300 and 700 C. while maintaining a pressure of at least atmospheres in said space and continuously removing products of the reaction.

47. The process of converting carbonaceous substances, such as solid and liquid fuels,

' distillation and extraction products thereof,

into valuable liquids which comprises treating them with added hydrogen and a catalyst comprising an oxide of a metal of the sixth group of the periodic system and heat at a temperature between about 300 and 700 C. and at a pressure of at least- 20 atmospheres.

48. The process of converting carbonaceous substances, such as solid and liquid fu els. distillation and extraction products thereof, into valuable liquids which comprises continuously feeding said substances with hydrogen into a reaction space containing an oxide of a metal of the sixth group of the eriodic system and held at a temperature etween about 300 and 7 00 C. while maintaining a pressure of at least 50 atmospheres in said space and continuously removing products of the reaction.

49. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with added hydrogen and a' catalyst comprising a compound of molybdenum and heat at a temperature between about 300 and 700 C. and at a pressure of at least 20 atmospheres.

50. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises continuously feeding said substances with hydrogen into a reaction space containing a compoundof molybdenumand held at a temperature between about 300 and 700 C. while maintaining a pressure of at least 50 atmospheres in said space and continuously removing products of the reaction.

51. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with added hydrogen and a catalyst comprising molybdenum oxide and heat at a temperature between about 300 and 7 00 C. and at a pressure of at least 20 atmospheres.

52. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises continuously feeding said substances with hydrogen into a reaction space containing molybdenum oxide and held at a temperature between about 300 and 700 C. while maintaining a pressure of at least 50 atmospheres in said space and continuously removing products of the reaction.

53. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with added hydrogen and a catalyst comprising a compound of chromium and heat at a temperature between about 300 and 700 C. and at a pressure of at least 20 atmospheres. I v

54. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable'liquids which comprises continuously feeding said substances with hydrogen into a reaction space containing a compound of chromium and held at a temperature between about 300 and 700 C. while maintaining a pressure of at least 50' atmospheres in said space and continuously removing products of the reaction.

55. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treat-" ing them with added hydrogen and a catalyst comprlsmg chromium oxide and heat at a temperature between about 300 and 700 C. and a pressure of at least 20 atmospheres.

56. The process of converting carbonaceous spbstances, such as solid and liquid fuels. distillation and extraction products thereof, into valuable liquids which comprises continu gusly feeding said substances with hydrogen. into a reaction space containing chromium oxide and held at a temperature between about 300 and 700 C. while maintaining a pressure of at least 50 atmospheres in said space and continuously removing products of the reaction. v

57. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids-which comprises treating them withadded hydrogen and up. catalyst comprising a compound of tungsten and heat at a temperature between about 300 and 700 C. and at a pressure of at least 20 atmospheres.

58. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises continuously feeding said substances, with hydrogen into a reaction space containing a compound of tungsten and held at a temperature between about 300 and 700 C. while maintaining a pressure of at least 50 atmos-- pheres in said space and continuously removlng products of the reaction.

' 59. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, intovaluable liquids which comprises treating them with added hydrogen and a.

taining a pressure of at least 50 atmospheres in said space and continuously removing products of the reaction.

In testimony whereof we our hands.

have hereunto set CARL KRAUCH. MATH IAS PIER. 

